Alkylation of hydrocarbons



Feb; 22, 1944.

J. DJYDANFORTH ALKYLATIQN OF HYDROCARBONS Filed Jan. 10, 1 941 moEzo u EATTQRNEY INVENTOR IIIIL. In I" I MHhs IIIIL H T R O A D U H P E S O .J

uaiui 2 .5553

Fatented Feb. 22, 1944 ALKYLATEON @F RYDROCABBONS Q Joseph lit.Daniorth, @hicago, ML, assignor to Universal cu Products Qompany,Ghicago, 11L, a

corporation of Delaware Application January it, ianfseun No. 373,960

cams. (e1. ace-asap This application is a. continuation-in-part of myco=pending application Serial Number 370,323, flied December 16, 1940.,

This invention relates to the treatment of isoparamnic hydrocarbons toproduce higher molecular weight alkyl derivatives thereof. Morespecifically the process is concerned with a method for alkylatingisoparaflinic hydrocarbons and other branched chain paramnichydrocarbons with oleflns in the presence of a volatile catalystintroduced by means of a substantially inert carrying fluid comprisingessentially one or more of the reactants charged to a reaction zonecontaining a packing material.

Alkylation of isoparaffinic hydrocarbons with oleflns may be effected inthe presence of easily volatilized catalysts including aluminumchloride-hydrogen chloride mixtures, boron fluoride hydrogen fluoridemixtures, hydrogen fluoride, etc. When an alkylation reaction is carriedout in the presence of a catalyst introduced as vapor it is necessaryfor a substantial proportion of the catalyst to be present in theallwlating reactor and consequently it is necessary to recycle largeamounts of the catalyst. Similar recycling of catalyst is necessary whenthe usual type of alkylation is carried out in liauidphase or in mixedphase as near the critical conditions where both gases and liquids maybe present in the reaction system. Iii order to substantially avoid therecycling of large amounts of catalyst, the reaction chamber employed inthe present process is filled with a granular packing material uponwhich a substantial proportion of the catalyst, carried thereto by afluid, is deposited and retained within the reaction zone. In this way arelatively high concentration of a catalyst is kept in the reaction Zonewhileintroducing the catalyst in relatively small amounts with thehydrocarbons or other fluids being charged to the akylation process,rather than. in the largeramount required to catalyze the reaction.

In one specific embodiment the present invention comprises a process forproducing higher boiling hydrocarbons which comprises subject- Accordingto the present invention isoparaffinic hydrocarbons including isobutaneand its homologs may be alkylated. The conditions of operation, however,may not necessarily be the same when alkylating isoparaflins and otherbranched chain paramn hydrocarbons of difierent reactivities. AlLoLthesealkylatable paraffins may be referred to broadly by the termisoparaffins. The olefins employed as alkylating agents are eithernormally gaseous or liquid and include e thyene, propene, butcnes,pentenes, hexenes, and higher olefins, the latter boiling generallywithin the approximate range of gasoline. The normally gaseous oleflnsgenerally combine directly with an isoparaifln during alkylation, whilehexenes and higher liquid olefins usually undergo depolymerization priorto or during alkylation with the result that two molecular proportionsof a substantially saturated alkylate are formed from two molecularproportions of an isoparamn and one molecular proportion of a hexene,while some 'still higher boiling olefinsmay depolymerize or split to agreater extent and form more than 2 molecular proportions of alkylationproducts. 1 I

The alkylation of an isoparaiflnic hydrocarbon with an olefin in thepresence of a volatile catalyst such as aluminum chloride or boronfluoride is generally aided by the presence of a hydrogen halide. Thushydrogen chloride generally is beneficial to the eflicient utilizationof aluminum chloride as catalyst and similarly the action of boronfluoride is improved by the presence of hydrogen fluoride. However,hydrogen fluoride alone may be utilized as a hydrocarbon alkylatingcatalyst and mixtures of aluminum chloride and boron fluoride may beemployed similarly. The addition of a substantially inert gas ashydrogen to a hydrocarbon mixture being subjected to alkylation mayimprove the operation of the process and increase the time during whichthe catalyst remains active.

By the process of this invention volatile atalytic materials as aluminumchloride, boron fluoride hydrogen fluoride, etc; may be introduced to apacked reaction zone by means of one or more of the fluids being chargedthereto. Thus in an alkylation in the presence of aluminum chloride, thealuminum chloride is picked up by a carrier fluid, which may behydrogen,

hydrogen chloride, a parafiinic hydrocarbon or a mixture of any two orall of these substances, from an aluminum chloride charging vessel whichis maintained under a temperature necessary to introduce into thecarrier fluid the desired amount of aluminum chloride. The aluminumchloride may be present in the charging vessel as a solid, a liquid, abinary or ternary mixture with other metal halides, or as an adsorbedlayer on an adsorbent material such as firebrick, charcoal, silica, etc.The mixture of aluminum chloride and isoparafilnic hydrocarbon with orwithout hydrogen and/or hydrogen chloride, is admixed with an olefin oran olefin-containing hydrocarbon fraction and the resultant mixture ischarged to a reaction zone containing a granular packing material whichmay or may not have been impregnated by aluminum chloride. While anolefin or an olefin-containing hydrocarbon is the preferred alkylatingagent, other substances as alkylhalides, alcohols, ethers, and estersmay be employed similarly for alkylating hydrocarbons.

The aluminum chloride catalyst is charged continuously with the otherreactants or inter mittently so that as the catalyst remaining upon thepacking material within the reaction zone becomes spent during use, afurther quantity of fresh aluminum chloride is introduced to thereaction zone containing the granular packing material which includessuch substances as porcelain, pumice, firebrick, quartz, activatedcharcoal, other activated carbons, diatomaceous earth, kaolin, raw andacid-treated clays, silica gel, alumina, magnesia, zirconia, titania,composites of silica with alumina and/or zirconia and metals possessingconsiderable surface as spongy iron. Halides of the Friedel-Crafts typeas those of aluminum, zinc, iron and copper may also be incorporatedwith any of the supporting materialsprior to being packed in thereaction zone, when such compositing is physically or chemicallyfeasible.

The alternative reactor filling materials are not necessarily equivalentin their-action and the particular granular filling material employed inany given alkylation reaction is dependent upon the hydrocarbons beingtreated, the temperature and pressure employed, the nature of thecatalyst charged, and other factors.

When relatively large reactors are employed it may also be desirable tointroduce aluminum chloride and the carrying fluid to a reactor atvarious points between the inlet and exit thereof so that the aluminumchloride is present in exactly the optimum concentration at all pointsthroughout the bed of granular filling material and also that no excessof aluminum chloride is present at the point of its introduction with aresulting deficiency of aluminum chloride at other points throughout thelength of the bed of reactor filling material.

It is proposed to carry out the alkylation of isoparaflins with olefinsin the presence of a volatilizable catalyst carried by one or more ofthe reactants into a packed reaction zone. When such alkylation iscatalyzed by aluminum chloride, the fluid material entering the catalystpickup chamber is heated to a temperature between about 150 and about350 F. and the subsequent alkylation reaction zone is preferablymaintained at a temperature between about 30 F. and about 300 F. under apressure of from substantially atmospheric to approximately 500 poundsper square inch. The preferred operating temperature for the allwlationreactor is generally between about and 200 F. and a preferred pressureabout 100 and 300 pounds per square inch.

In such a process where a reactant is substantially saturated with avolatile or soluble catalyst at one temperature and is then caused toreact with a second substance at a relatively lower temperature, it isadvantageous to divide the stream of the first reactant into two parts,to saturate one part with the catalyst at the higher temperature, andthen'to combine the heated and unheated partsof the first reactant withthe second reactant to form a mixture of desired temperature forsubsequent catalytic treatment.

In the hydrocarbon mixture subjected to alkylation it is preferable tohave a relatively high molecular ratio of isoparafiln to olefin, with anolefin concentration generally between about 1 and 25 mole per cent, inorder to substantially avoid olefin polymerization and to favoralkylation. Hydrogen chloride is preferably present in the alkylationmixture generally to the extent of up to about 5 mole per cent of thetotal hydrocarbon mixture' subjected to contact with the alkylatingcatalyst. It is also recommendedto add hydrogen to the reaction mixture,generally in a quantity of not more than about 20 mole per cent of thetotal hydrocarbons.

The hydrogen and/or hydrogen chloride charged to alkylation may also beused for carrying thereto the aluminum chloride as it is generallydesirable to carry the aluminum chloride by means of a fluid having arelatively low reactivity therewith. The paraflinic hydrocarbon may alsobe employed as a carrier but the olefin is less desirable for thispurpose because of its ,tendency to undergo polymerization in thepresence of aluminum chloride especially if hydrogen chloride or watervapor is present.

Other types of hydrocarbons as aromatics and naphthenes may be alkylatedsimilarly with oleflns and the other above mentioned alkylating agentsin the presence of a volatilizable or soluble catalyst introducedcontinuously by means of a fluid to a reaction zone containing asubstantially inert packing material.

While a gas is preferably used as the fluid for carrying the catalyst tothe packed reaction zone, a liquid may be employed similarly, althoughnot necessarily under the same operating conditions. In the latter casethe catalyst as aluminum chloride is dissolved and/or dispersed in oneor more of the liquid reactants and the resulting solution and/ordispersion is thereafter charged to a reaction zone containing a packingmaterial which retains in said reaction zone a substantial proportion ofthe catalytic material charged thereto. In this way it is also possibleto maintain a relatively high concentration of catalytic material in areactor to which more catalyst is introduced with the charge toreplenish the loss of catalyst by sublimation and/or by solution in thereaction mixture.

The alternative means which may be used for introducing a catalyst to apacked reaction zone by a fluid carrying medium are not necessarilyequivalent and the particular means employed in any specific case dependupon the properties of the hydrocarbons undergoing treatment, the natureof the catalyst, the conditions of operation, and other factors. 7

For the purpose of illustrating the combination of steps characteristicof the present invention,

the accompanying drawing shows diagrammatically one form of apparatussuitable for use in producing a more valuable hydrocarbon product byalkylating an isoparaflin with an olefin in a packed reaction zone inthe presence of a volatile catalyst carried thereto by one or more ofthe charged reactants. It is understood that other types of apparatusmay also be used for carrying out the process and that there are othermethods of introducing a catalyst as by mechanically adding catalystpowder or by extruding into the system a paste-like material containingaluminum chloride. Also variations in the order oil-mixing the reactingcomponents may be employed in the process.

Referring to the drawing, a hydrocarbon fraction containing isoparaflinsis admitted through line I and valve 2 topump 3 which discharges throughline 4 containing valve 5. At least a portion of theisoparaihn-containing fraction is directed from line 4 through line 6,valve I, and coil 8 which receives heat from heater 9 and thence throughline ID to catalyst pick-up chamber H containing aluminum chloride as asolid, liquid, an adsorbed layer on an adsorbent such as firebrick, oras a binary or ternary mixture with other metal halides. In chamber IIthe temperature, pressure, and amount of isopara'ffin-containinghydrocarbon fraction passing therethrough are controlled so as to pickup aluminum chloride in an amount desired for use as catalyst in asubsequent alkylation treatment as hereinafter set forth. I

Although only one catalyst pick-up chamber is shown in the attacheddiagrammatic drawand the picked-up aluminum chloride is directed throughline H containing valve 13 and is commingled in line it, by meanshereinafter set forth, with an olefin-containing hydrocarbon fraction,fresh and recycled hydrogen and hydrogen chloride, a recycled fractioncontaining unconverted isoparafiin hydrocarbons, arid, when desired, aportion of the isoparaflin-containing hydrocarbon fraction charged tothe process.

Hydrogen and/or hydrogen chloride are introduced to line I l containingvalve l under a suitable pressure by a pump, compressor, or other means,not shown; an olefin or an olefin-containing hydrocarbon fraction isadmitted through line it and valve H to pump or compressor it whichdischarges through line l9 and valve 2@ into line I4; and a recycledmixture of hydrogen and hydrogen chloride is directed through line 65containing valve 66 to the line M from which the mixture containedtherein is directed through line i2 and thence to reactor 2| containinga granular packing material. Chamber Ii may also be heated by any othersuitable means and reactor 2| may be fitted with a meansof cooling ifthis is necessary to maintain the temperature needed for the alkylationreaction. I Also, the mixture containing isoparafiins, aluminumchloride, olefins, hydrogen, and hydrogen chloride being directed toreactor 2| by way of line i2 is therein commingled with a fractionconline l2 to reactor 2| containing a granular filling material whichmay consist of any one'or a number of materials as aforementioned.

When desired, paraffins, isoparamns, hydrogen, and/or hydrogen chloridemay be used singly or in any combination to carry aluminum chloride fromcatalyst pick-up chamber throu h line i2 to reactor 2|- containing asuitable packin material. When hydrogen chloride is charged to catalystpick-up chamber ll simultaneously with a paraflin fraction containingnormal and/or mildly branched chain parafilns, a substantial amount ofparaifin isomerization may occur in the cataiyst pick-up chamber in thepresence of 1 aluminum chloride to form mildly branched chain paraflinsfrom normal parafiins, and more-highly branched chain paraflins from themildly branched chain parafilns. When such preliminaryisomerization'occurs, the resulting branched chain parafllns may bealkylated with oleflns in reactor 2| simultaneously with the alkylatlonof the branched chain parailins and other alkylatable hydrocarbonspresent in the fraction charged to the process.

Such alternative means of carrying and introducing aluminum chloride toa packed alkylating reactor are not necessarily equivalent and theparticular aluminum chloride carrying means chosen in any given case aredependent upon the reacting hydrocarbons, the amount of catalystemployed, the conditions of operation, and other factors.

The products from reactor 2| are directed through line 22 and valve 23to separator 24 in which some relatively heavy residue or sludgecontaining partially spent aluminum chloride is separated and withdrawnthrough line 25 and valve 26. The products passing through line 22 maybe cooled, by means not shown, and/or treated to remove aluminumchloride, as by scrubbing with a molten salt as a mixture of anothermetal halide and aluminum chloride or by passage through a vesselcontaining a granular adsorbent, prior to admission to separator 26.Although separator 24 is shown diagrammatically as one vessel, two maybe employed so as to have one in use while the other is being cleaned.

When desired, the relatively heavy residue or sludge containingpartially spent aluminum chloride may be subjected to contact, by meansnotparafiins comprising both normal and branched chain isomers, andsubstantially free from olefinic hydrocarbons, may thereafter besubjected to con tact with aluminum chloride to pickup and carry to thepacked reaction zone the desired amount of aluminum chloride. Thealuminum chloridecontaining sludge may alternatively berecycled Themixture of products containing a substantlally saturated alkylate formedfrom olefins and from a portion of the isoparaffln hydrocarbons as wellas the excess of the isoparaflin-containing fraction, hydrogen, andhydrogen chloride employed in the alkylation step is passed through line21 and valve 28 to fractionator 29 of conventional design in which alight fraction containing hydrogen and hydrogen chloride issubstantially separated from higher boiling hydrocarbons. When it isdesirable to operate fractionator 29 under a pressure above thatemployed in alkylation reactor 2| in order to assist in the separationof the reactants and products and to facilitate recycling of said lightfraction and of unconverted paramns, valve 28 is closed and the mixtureof hydrocarbons, hydrogen, and hydrogen chloride is passed from line 21through line 30 and valve 3| to pump 32 which discharges through line 33and valve 34 into fractionator 29.

From fractionator 29 a light fraction containing hydrogen, hydrogenchloride, and relatively small amounts of normally gaseous parailins, asmethane, ethane, propane, and butanes, is taken overhead through line 35and valve 38 to condenser 31 and thence through run-down line 38 andvalve 39 to receiver 40 equipped with conventional gas release line 4|containing valve 42 and with liquiddraw-ofi line 43 containing valve 44.At least a portion of a normally gaseous mixture comprising essentiallyhydrogen, hydrogen chloride and some methane is directed from near thetop of receiver 40 through line 45 and valve 46 to line l4, alreadymentioned, in which fresh hydrogen and hydrogen chloride are commingledwith other reactants later conducted through line l2 to alkylationreactor 2 I. 1

Although the isoparaflin-contaimng fraction contained in line 4 isindicated in the attached diagrammatic drawing as the carrying fluid forthe aluminum chloride catalyst, it may also be desirable to introduce tothe fraction in line 4 by way of line 41 and valve 48 a portion of themixture containing hydrogen and hydrogen chloride being recycled throughline 45, aforementioned. A portion of the material present as liquid inreceiver 40 is directed therefrom through line 49 and valve 50 to pumpwhich discharges through line 52 and valve 53 into the upper portion offractionator 29 to assist in controlling the temperatures therein.

From the bottom of fractionator 29 a normally liquid mixture comprisingessentially a substantially saturated alkylate and an unconvertedisoparaflln-containing hydrocarbon fraction is directed through line 54and valve 515 to fractionator 56 of conventional design in which theunconverted isoparafllnecontaining fraction is separated from asubstantially saturated alkylate-containing fraction of gasoline motorfuel boiling range, the latter being withdrawn to storage through line51 and valve 58.

The unconverted isoparaflin-containing hydrocarbon fraction is passedoverhead through line 59, valve 60, condenser 6|, and run-down line 52containing valve 63 to receiver 64 equipped with conventional gasrelease line 65 containing valve 66. A portion of the condensab inreceiver .54 is withdrawn therefrom through line 61 and valve 68 by pump69 which discharges through line and valve II into the top offractionator 56 to assist in controlling'the temperatures therein. Theremainder of the condensate contained in receiver 64 and comprisingessentially the excess of isoparailln-containing fraction unconverted inthe alkylation, is recycled through line '12 and valve 13 to line=l2,-already mentioned. A

' portion of the freshly charged isoparaflin-containing fraction may beintroduced to line 12 from line 4, thus by-passing the catalyst pick-upchamber l I.

The following examples are introduced as characteristic of the practicaloperation of the process. although they are presented with no intentionof limiting the scope of the invention in exact correspondence with thenumerical data since some latitude is possible in the choice of the typeof reactor packing material, the amount of catalyst, the conditions ofoperation, etc.

EXAMPLE I 110 parts by weight (200 volumes) of a hydrocarbon fractioncontaining 3.8 mole per cent propane, 74.7% isobutane, and 21.5% normalbutane, and 2 parts by weight of hydrogen chloride was passed downwardlyper hour through a chamber containing 113 parts by weight of aluminumchloride granules maintained at 200 F. and-under a pressure of 200pounds per square inch in order to pick-up in the fluid hydrocarbons adesired amount of aluminum chloride. The resulting mixture ofhydrocarbons, hydrogen chloride, and aluminum chloride was passeddownwardly through a subsequent reaction zone containing volumes offormed pieces of porcelain packing material and maintained at 150 F.After charging the iso-butane-containing fraction for onehalf hour,ethylene was also introduced to the reaction zone at an hourly ratesufllcient to give a reaction mixture containing approximately 10 moleper cent of ethylene.

A runfor a total of 45 hours yielded a total of 527 parts by weight (722volumes) of a substantially saturated alkylate containing 169 volumes ofpentanes, 472 volumes of hexanes with 91 cctane number, and 81 volumesof higher boiling grams (200 cc.) of the paraflin hydrocarbon fractioncharged in Example I was passed per hour upwardly through a steelreactor containing 200 grams (173 volumes) of 4-20 mesh aluminumchloride maintained at 205 F. under a pressure of 250 pounds per squareinch. The resulting mixture of hydrocarbons and aluminum chloride wasdirected from the top of the first chamber containing aluminum chlorideto a reaction zone containing 100 volumes of porcelain packing materialas used in Example I maintained at a temperature between about and about180 F. as indicated in Table I. At

thebeginning of a run the isobutane-containing fraction was charged forfrom about 4 to 8 hours the solid aluminum chloride.

presence of aluminum chloride Team: I

introduced by the isobutane to a packed reaction zone Period No.

1 2 a 4 t 1 s 1 Dunflon 110111! 48 27 a 24 17 25 24 18 Temp. 0! packedreactor JR. 1 0 150 A150 160 100 170 170 180 0 stock, mole per cent:ghyjgnn 9. 0 n. a 13. 1 18.0 19.9 19. V20. 7 11. 7 Bntanes, mainlg iso-3 83- 1 81-9 77. l 75. 0 70. 3 75. 1 78. 1 Hydrogen ch10 do 1- 8 L 3 L2 1. 2 1. 2 1. 2 1. 2 1. 1 Hydrogen 0. 0 c 0 0.1 0.7 0.0 0. 0 0. 0 0. 0w Pi l-2 :3 d 3. 6 3. 2 3. 0 3.0 3.0 3. 0 8. 0 3. 1

e nee, grams charge 0,011 3,450 3,410 0,001 2,244 2,900 3,079 2, 421Butanee- 710 245 250 2. 0 2, 000 2, 650 2, 730 2, 190 Ethylene- 307 211226 281 244 316 349 231. Liquid product: V

Total grams. 413 499 600 651 300 481 310 279 Weight per cent ethylenecharged 1 237 221 204 14B 152 86 121 't'ireig l i t per cent ethylenereacted 237 237 m1 190 176 168 102 215 Dist t on, vol. per cent- 70-105"F.- 18 10 10 0 0 12 7 lot-150 F.- 00 02 06 74 00 50 66 03 Above 160 F 2219 34 28 31 32 32 30 Oleflns in exit gas, moi per cent: After 4 hours7.9 0 0; 8 6. 6 3. 8 16. o 13 The above table shows how the completeness5 renewedamount of freshly volatilized aluminum oi the alkylationreaction is affected by the proportion of ethylene present in thereaction mixture charged together with aluminum chloride and hydrogenchloride to a packed reaction zone. Thus after a short time on test, anolefin-free exit gas was obtained in period 1 and the ethyl- 4 oneremoval continued to be complete until period 4 when the olefinconcentration in the charge reached 18%. when the total chargecontained. more than 18% of ethylene, part of this olefin appeared inthe exit gas at all times.

The chief diflerence in the nature of the liquid product obtained as theconcentration of ethylene in the charge was increased consisted in anincrease in the percentages of alkylation products boiling higher thanhexanes at the expense oithe pentane production, while the yield ofhexanes remained fairly constant. The alkylation products boiling higherthan hexanes contained a substantial proportion of octanes probablyformed by the alkylation of hexanes with ethylene. The hexane fractionsobtained in the different periods of ths run had zero bromine number andcontained between about 0.02 and about 0.05 per cent of chlorine.

In previous runs, hydrogen chloride was introduced into the aluminumchloride pick-up chamber or vaporizer along with the isobutane. Such a.procedure caused the iormation of some sticky, lower-layer material uponthe surface of In the present run, hydrogen chloride was not introducedinto the vaporizer but only into the reactor with the result thataluminum chloride recovered from the vaporizer was free from stickymaterial and as bright in color as that of the fresh aluminum chloride.

At the end of the run when mea was taken apart, considerable lower-layermaterial was found distributed throughout the packed reaction zone andthe remainder of the system. This material was in the form of a darkbrown sludge which flowedreadily until it was exposed to air, and whentreated with water it reacted violently thus indicating that it wasstill active.

EXAMPLE m A number of runs were made on the allrylation of isobutanewith isobutene in the presence 01 aluminum chloride, in the form of aconstantly chloride continuously deposited upon a ceramic packingmaterial contained in a reaction zone. The results obtained, which areshown in more detail in Table 11, indicated that the lower temperaturesgave the greater yields of lower boiling materials'havlng low brominenumbers than did higher temperatures. Good results were obtained whenisobutane was pumped upwardly through a tube containing 150 grams of4-20 mesh aluminum chloride maintained at 200 F.- and the resultingmixture was thereafter intro duoed to a packed reaction zone maintainedat F. to which lsobutene and hydrogen chloride were also admitted.

Tears II Alkylotion of isobutane with. isobutene Period N0.

Duration ..hours.. 96 24 24 24 24 48 Temperature of packed reactor .F..150 130 100 ressuret of packed reac or 200 220 220 220 250 250 Chargingstock, composiposition, mole per cent:

Isobutanc 70. 9 70. 0 71. 0 70.9 69. 7 70. 0 n-Butaue l6. 6 16. 4 16. 6'16. 5 16. 7 l6. 7 P10138112 2.0 2.0 1.9 2.0 2. 5 2. 4 Pentancs 0. 0 0.0 0. 0 0. 0 0. 5 0. 5 Isobutene 8. 4 9. 0 8. 5 8. 5 9. 0 8. 9 Hydrogenchloride 2. 2 2.0 2. 0 2. l 1. 6 1. 5 Charging rates:

Peraifln Iced- ..cc.lhr 198 203 201 195 203 206 Isobutene feed ec.lhr-19. 5 21. 3 20. 0 19. 2 21. 4 21. 6 Hydrogen chloride .l l.- 1. 75 1.60 1. 60 1. 60 1. 35 1. 35 Mole ratio, isobutane/ isobutenc 8.4 7. 0 8.4 8.4 7. 8 7.8 Mole ratio, total buta eslisobute e 10.4 9.7 10:3 10.39.6 9.7 Liquid products, pentanes and higher hydrocarbogs:

rams; 1,517 384 313 275 309 l, 24 Yield, based on iso- 0 butane chargedweight per cent" 157 144 126 115 116 Bromine number 21 10 28 36 42 7Thus in period 6 with an hourly charge consisting of approximately 112grams of a subst: :1- tially isobutane fraction, 1.35 grams of hydrogenchloride, and sumcient isobutene to provide approximately 8.9 mole percent of this hydrocarbon in the total hydrocarbon mixture charged,

only 0.02% chlorine, and had a bromine number The novelty and utility ofthe process of this invention are evident from the precedingspecification and examples given, although neither section is intendedto unduly limit its generally broad scope. v

I claim as my invention: 1. In the alkylation of hydrocarbons, themethod which comprises reacting an alkylatable hydrocarbon with analkylating agent in a reaction zone containing a solid packing material,dissolving an alkylating catalyst in a liquid which is substantiallyunreactive with the catalyst, introducing the resultant solution of saidliquid and catalyst to said zone and collecting a substantial portion ofthe catalyst on said packing material. 2. In the alkylation ofhydrocarbons wherein an isoparaflin is reacted with an olefin in areaction zone containing a solid packing material, the method whichcomprises contacting at least a portion of said isoparafiin, in Qiquidphase, with a metal halide catalyst of the Friedel-Craits type underconditions such as to form a solution of metal halide catalyst in theliquid isoparaiiin, the

This liquid product contained 73% latter being substantially unreactivewith the catalyst under said conditions, introducing said solution ofliquid isoparafiin and catalyst to the reaction zone, and depositing asubstantial portion of the catalyst on said packing material.

3. An alkylation process which comprises contacting a liquid with a bodyof metal halide catalyst of the Friedel-Crafts type under conditionssuch as to dissolve a portion of said body in the liquid, said liquidbeing substantially unreactive with the metal halide catalyst under saidconditions, introducing the resultant solution to a reaction zonecontaining a solid packing material and depositing a substantial portionof the catalyst on said packing material, simultaneously introducing analkylatable hydrocarbon and an alkylating agent to said zone and thereinreacting the same in the presence of the catalyst.

4. The process as defined in claim 3 further characterized in that saidliquid comprises at least a portion of said alkylatable hydrocarbon.

5. An alkylation process which comprises contacting an isoparaflin, inliquid phase, with aluminum chloride under conditions such as todissolve aluminum chloride in the isoparaflinic liquid without anyappreciablechemical reaction between the isoparaflin and the aluminumchloride, introducing the resultant solution into a reaction zonecontaining a solid packing material and depositing aluminum chloridefrom the solution onto the packing material, simultaneously introducingan olefin to the reaction zone and therein reacting the same with atleast a portion of the isoparaflin in the presence of the depositedaluminum chloride.

JOSEPH D. DANFORTH.

